Thin films composed of poly(ethylene imine)-functionalized single-walled carbon nanotubes (CNTs) were formed through a vacuum filtration process and decorated with Au nanoparticles, roughly 40 nm in diameter. The Au nanoparticles, on the surface of the CNT fabric, accommodated the growth of GaAs nanowires (NWs), according to the vapour-liquid-solid (VLS) mechanism, in a gas-source molecular beam epitaxy (GS-MBE) system. Structural analysis indicated that the nanowires, up to 2.5 μm in length, were not preferentially oriented at specific angles with respect to the substrate surface. The NWs grew in the energetically favored  direction of the wurtzite lattice while stacking faults, characterized as zincblende insertions, were observed along their lengths. Micro-photoluminescence spectroscopy demonstrated bulk-type optical behaviour. Current-voltage behaviour of the core-shell pn-junction heterostructured NWs exhibited asymmetric rectification. Thus, the potential for the incorporation of such hybrid NW/CNT architectures into an emerging class of flexible opto-electronic devices is demonstrated.